Chapter

12
Cold-End Corrosion

during Service

Locations
Cold-end corrosion will occur wherever the temperature of metal drops
below the sulfuric acid dew point of the flue gas. Most problems caused by
cold-end corrosion occur in relatively low temperature boiler components
such as the economizer, air preheater, induced-draft fan, flue-gas scrub-
bers, and stack.

General Description
In most combustion systems, flue-gas temperatures can range from 300O0F
(165O0C) in the flame to 25O 0 F (1210C) or less at the stack. This tempera-
ture change can cause numerous chemical and physical changes in the
components of the flue gas. Among the most troublesome changes is the
reaction between water vapor and sulfur trioxide to form sulfuric acid.
As flue gas cools, vapor-phase sulfuric acid forms. If the sulfuric acid
vapor contacts a relatively cool surface, it may condense as liquid sulfuric
acid. The temperature at which sulfuric acid first condenses (sulfuric acid
dew point) varies from 240 to 330 ° F (116 to 166 ° C) or higher, depending on
sulfur trioxide and water-vapor concentrations in the flue gas. The corro-
sion resulting from condensation of sulfuric acid on metal surfaces is
termed "cold-end corrosion" because it generally affects the cooler regions
of the combustion system.
In general, the problem is associated with the combustion of fuel that
contains sulfur or sulfur compounds. Sulfur in the fuel is oxidized to sulfur
trioxide in the following sequence:

S + O2 -»SO2

A small fraction (1% to 3%) of the sulfur dioxide produced is additionally

oxidized to sulfur trioxide by direct reaction with atomic oxygen in the
flame:

SO2 + O -» SO3

Catalytic oxidation to SO3 is also possible if ferric oxide, vanadium pen-

toxide, or nickel is present:

SO2 + %O2 + catalyst -> SO3

The quantity of sulfur trioxide and moisture in the flue gas affects the
temperature at which the dew point is reached. The graph in Fig. 12.1
illustrates the general relationship between sulfur trioxide concentration
and dew point.
Corrosion may occur wherever metal temperatures are less than the

Figure 12.1 Relationship between SO3 levels in flue gas and

sulfuric acid dew point.
sulfuric acid dew point. Below this dew point, sulfuric acid forms on metal
surfaces and corrodes the metal according to the following reaction:
H2SO4 + Fe -» FeSO4 + H 2 T
Note that it is the temperature of the metal, not the temperature of the flue
gas, that is critical. Even though the flue-gas temperature is well above the
dew point, corrosion is a distinct possibility wherever metal temperatures
are less than the dew point.

Critical Factors
The critical factors governing cold-end corrosion include the presence of
corrosive quantities of sulfur trioxide, the presence of moisture in the flue
gas, and the presence of metals whose surface temperature is below the
sulfuric acid dew point.
The amount of sulfur trioxide produced increases with increases in the
level of excess air, gas residence time, gas temperature, amount of catalyst
present, and sulfur level in the fuel (Fig. 12.2).
The amount of moisture produced is dependent on many factors.
Sources include moisture content in the fuel, fuel combustion, leaks in
boiler tubes, and steam from soot blowing.
A metal whose surface temperature is below the sulfuric acid dew point is
susceptible to cold-end corrosion. The dew point increases as the quantity
of sulfur trioxide in the flue gas and the moisture content of the flue gas
increase.
The severity of cold-end corrosion is most extreme with "sour" gaseous
fuels, while it is less extreme with oil. Severity of corrosion is least with
coal. The combined burning of sulfur- and vanadium-containing fuel oil

Figure 12.2 Relationship between the percentage of sulfur

in fuel oil and flue-gas dew point.
with natural gas is worse than use of oil alone because of the high water-
vapor content that results from burning of natural gas.

Identification
Cold-end corrosion frequently produces general, smooth, featureless metal
loss. Rough, rust-colored surfaces also may be observed.

Elimination
Elimination of cold-end corrosion is achieved by gaining control of the
critical factors that govern it. The critical factors include the presence of
corrosive quantities of sulfur trioxide in flue gas, the presence of excessive
quantities of moisture in the flue gas, and the presence of metals whose
surface temperature is below the sulfuric acid dew point.
To eliminate the presence of corrosive quantities of sulfur trioxide in
flue gas it is necessary to operate the boiler at or below 5% excess air to the
burners, to minimize air infiltration, and to specify fuels with low sulfur
content.
To eliminate the presence of excessive quantities of moisture in the flue
gas, it is necessary to specify fuel with low moisture content, to prevent
tube leaks, and to reduce the amount of soot blowing.
Substantial design changes are often required to eliminate metals with
surface temperatures below the sulfuric acid dew point. These design
changes are beyond the scope of this manual.
In boilers equipped with multiple air preheaters it is possible to isolate
and perform an on-line washing of one of the preheaters.
Feeding of fuel additives and/or cold-end additives constitutes a chemi-
cal solution to this problem.

Cautions
Metal surfaces that have suffered cold-end corrosion may be covered with
deposits and/or corrosion products, making visual identification difficult.
In addition, cold-end corrosion typically produces smooth, uniform, fea-
tureless metal loss, such that the attacked surfaces closely resemble the
original, unaffected surface contour. Thickness measurements using ul-
trasonic techniques serve as a nondestructive means of evaluation. Visual
comparison of surface profiles and metal thicknesses on a section cut from
the equipment may also reveal the occurrence of cold-end corrosion.
CASE HISTORY 12.1

Industry: Pulp and paper

Specimen Location: Economizer, recovery boiler
Specimen Orientation: Vertical
Years in Service: 20
Drum Pressure: 600 psi (4.1 MPa)
Tube Specifications: 21/2-in. (6.3 cm) outer diameter
Fuel: Black liquor

Figure 12.3 is a close-up photograph of the external surface of an economizer

tube that has sustained general corrosion. Note the pockmarked contour.
Corrosion occurred in regions of the economizer where sulfuric acid con-
densed from the flue gas. Such condensation, if it occurs, generally affects
the tubes at the end of the economizer where feedwater enters — i.e., the end
where metal temperatures are lower.

Figure 12.3 Pockmarked contour of economizer tube exposed to condensed sulfuric acid.
(Magnification: 7.5 X.)
CASE HISTORY 12.2

Industry: Sugar
Specimen Location: Economizer
Specimen Orientation: Horizontal
Tube Specifications: 1% in. (4.8 cm) outer diameter
Fuel: No. 6 fuel oil (1.9% S)

The corrosion and perforations apparent in Fig. 12.4 represent a chronic

problem in this boiler. The external surface, including fin surfaces, exhibited
smooth, general metal loss. In many cases, severe corrosion along the
attachment line had caused the fins to separate from the tube wall.
The deposits and corrosion products covering the corroded surfaces were
analyzed by #-ray diffraction and identified as hydrated iron sulfate. The pH
of a 1% slurry of the material was measured at 2.3. The corrosion was caused
by condensation of sulfuric acid on the cold tube surfaces during boiler
operation.

Figure 12.4 Corrosion and perforations of finned economizer tube resulting from exposure to
condensed sulfuric acid. Note detachment of fins from tube wall.